Germanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions

ABSTRACT

Molecular sieve compositions having three-dimensional microporous framework structures of GeO 2 , AlO 2 , PO 2  and SiO 2  tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: 
     mR:(Ge w  Al x  P y  Si z )O 2   
     wherein &#34;R&#34; represents at least one organic templating agent present in the intracrystalline pore system; &#34;m&#34; represents the molar amount of &#34;R&#34; represent per mole of (Ge w  Al x  P y  Si z )O 2  ; and &#34;w&#34;, &#34;x&#34;, &#34;y&#34; and &#34;z&#34; present the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as absorbents, catalysts, etc. is also disclosed.

This application is a continuation-in-part of our copending application Ser. No. 599,971 filed Apr. 13, 1984, now abandoned.

FIELD OF THE INVENTION

The instant invention relates to a novel class of crystalline microporous molecular sieves, to the method of their preparation and to their use as adsorbents and catalysts. The invention relates to novel germanium-aluminum-phosphorus-silicon-oxide molecular sieves containing framework tetrahedral oxide units of germanium, aluminum, phosphorus and silicon. These compositions may be prepared hydrothermally from gels containing reactive compounds of germanium, aluminum, phosphorus and silicon capable of forming framework tetrahedral oxides, and preferably at least one organic templating agent which functions in part to determine the course of the crystallization mechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline aluminosilicate silicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO₂ and SiO₂ tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.

Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO₂ tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6Å or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO₂ and PO₂ tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.

In U.S. Pat. No. 4,440,871, there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensional crystal framework of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:

mR:(Si_(x) Al_(y) P_(z))O₂

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.

In U.S. Pat. No. 4,500,651, there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:

mR:(Ti_(x) Al_(y) P_(z))O₂

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.

In U.S. Pat. No. 4,567,029, there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO₂, AlO₂ and PO₂ tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(M_(x) Al_(y) P_(z))O₂

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y", and "z" represent the mole fractions of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.

In U.S. Pat. No. 4,544,143, there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO₂, AlO₂ and PO₂ tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula

mR:(Fe_(x) Al_(y) P_(z))O₂

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fractions of the iron, aluminum and phosphorus, respectively present as tetrahedral oxides.

The instant invention relates to new molecular sieve compositions comprising framework tetrahedral units of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class of germanium-aluminum-phosphorus-silicon-oxide molecular sieves having a crystal framework structure of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts. The members of this novel class of compositions have crystal framework structures of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. These molecular sieve compositions comprise crystalline molecular sieves having a three-dimensional microporous framework structure of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units. The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including the aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of certain species and by the existence of species heretofore unknown for binary and ternary molecular sieves.

The molecular sieves of the instant invention will be generally referred to by the acronym "GeAPSO" to designate the framework of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiOl₂ tetrahedral units. Actual class members will be identified by denominating the various structural species which make up the GeAPSO class by assigning a number and, accordingly, are identified as "GeAPSO-i" wherein "i" is an integer. This designation is an arbitrary one and is not intended to denote structural relationship to another material(s) which may also be characterized by a numbering system.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class of germanium-aluminum-phosphorus-silicon-oxide molecular sieves comprising a crystal framework structure of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts.

The GeAPSO molecular sieves of the instant invention comprise a framework structure of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3, but is preferably not greater than about 0.15; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of FIG. 1. Points A, B, C, D and E of FIG. 1 have the following values for "w", "x", "y", and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z + w                                            ______________________________________                                         A        0.60          0.38   0.02                                             B        0.38          0.60   0.02                                             C        0.01          0.60   0.39                                             D        0.01          0.01   0.98                                             E        0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the GeAPSO molecular sieves the values of "w", "x", "y" and "z" in the above formula are within the hexagonal compositional area defined by the points a, b, c, d, e and f of the ternary diagram which is FIG. 2 of the drawings, said points a, b, c, d, e and f representing the following values for "w", "x", "y" and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z + w                                            ______________________________________                                         a        0.60          0.38   0.02                                             b        0.38          0.60   0.02                                             c        0.01          0.60   0.39                                             d        0.01          0.39   0.60                                             e        0.39          0.01   0.60                                             f        0.60          0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the GeAPSO molecular sieves the values of "w", "x", "y" and "z" in the above formula are within the hexagonal compositional area defined by the points g, h, i, j, k and l of the ternary diagram which is FIG. 2 of the drawings, said points g, h, i, j, k and l representing the following values for "w", "x", "y" and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x             y      z + w                                            ______________________________________                                         g        0.60          0.35   0.05                                             h        0.47          0.48   0.05                                             i        0.40          0.48   0.12                                             j        0.40          0.36   0.24                                             k        0.46          0.30   0.24                                             l        0.60          0.30   0.10                                             ______________________________________                                    

The GeAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.

GeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of germanium, aluminum, phosphorus and silicon, preferably an organic templating, i.e., structure-directing agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure, at a temperature between 50° C. and 250° C., and preferably between 100° C. and 200° C., until crystals of the GeAPSO product are obtained, usually for a period of from several hours to several weeks. Effective crystallization times of from about 2 hours to about 30 days are generally employed with from about 4 hours to about 20 days, and preferably about 12 hours to about 7 days, being typically employed. The product is recovered by any convenient method such as centrifugation or filtration.

In synthesizing the GeAPSO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:

aR:(Ge_(r) Al_(s) P_(t) Si_(u))O₂ :bH₂ O

wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and desirably not greater than 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20 and desirably not greater than about 10; and "r", "s", "t" and "u" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions "r", "s", "t" and "u" are generally defined as being within the pentagonal compositional area defined by points F, G, H, I and J of the ternary diagram of FIG. 3. Points F, G, H, I and J of FIG. 3 have the following values for "r", "s", "t" and "u":

    ______________________________________                                         Mole Fraction                                                                  Point   s             t      (u + r)                                           ______________________________________                                         F       0.60          0.38   0.02                                              G       0.38          0.60   0.02                                              H       0.01          0.60   0.39                                              I       0.01          0.01   0.98                                              J       0.60          0.01   0.39                                              ______________________________________                                    

Especially preferred reaction mixtures are those containing from about 0.2 to 0.3 total moles of germanium and silicon, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "r", "s", "t" and "u" such that (r+s+t+u)=1.00 mole, whereas in the examples the reaction mixtures are expressed in terms of molar oxide ratios normalized to the moles of Al₂ O₃ and/or P₂ O₅. This latter form is readily converted to the former form by routine calculations by dividing the number of moles of each component (including the template and water) by the total number of moles of germanium, aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.

In forming reaction mixtures from which the instant molecular sieves are formed the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorus and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium and quaternary ammonium compounds, the latter two being represented generally by the formula R₄ X⁺ wherein "X" is phosphorus or nitrogen and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired GeAPSOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include tetramethylammonium; tetraethylammonium; tetrapropylammonium; and tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of GeAPSO, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direct the formation of several GeAPSO compositions, and a given GeAPSO composition can be produced using several different templating agents.

The reactive phosphorus source is preferably phosphoric acid, but organic phosphates such as triethyl phosphate have been found satisfactory, and so also have crystalline or amorphous aluminophosphates such as the AlPO₄ composition of U.S. Pat. No. 4,310,440. Organophosphorus compounds, such as tetrabutylphosphonium bromide, do not, apparently, serve as reactive sources of phosphorus, but these compounds do function as templating agents. Conventional phosphorus salts, such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.

Almost any reactive silicon source may be employed such that SiO₂ tetrahedral units are formed in situ. The reactive silicon source may be silica in the form of a silica sol, may be a fumed silica or may be other conventional sources of silica used in zeolite synthesis such as reactive solid amorphous precipitated silicas, silica gel, alkoxides of silicon, tetraalkyl orthosilicates (for example, tetraethyl orthosilicate), silicic acid, alkali metal silicates and the like.

The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.

The reactive source of germanium can be introduced into the reaction system in any form which permits the formation in situ of a reactive form of germanium, i.e., reactive to form the framework tetrahedral oxide unit of germanium. Compounds of germanium which may be employed include oxides, alkoxides, hydroxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates (e.g., acetates) and the like. Especially preferred sources of germanium are germanium tetrachloride and germanium ethoxide.

As illustrated in some of the Examples below, in some cases it may be advantageous, when synthesizing the GeAPSO compositions of the present invention, to first combine sources of germanium and aluminum, or of germanium, aluminum and silicon, to form a mixed germanium/aluminum or germanium/aluminum/silicon compound, typically a mixed germanium/aluminum or germanium/aluminum/silicon oxide, and thereafter to combine this mixed germanium/aluminum or germanium/aluminum/silicon compound with a source of phosphorus to produce the final GeAPSO composition.

While not essential to the synthesis of GeAPSO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the GeAPSO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.

After crystallization the GeAPSO product may be isolated and advantageously washed with water and dried in air. The as-synthesized GeAPSO generally contains within its internal pore system at least one form of the templating agent employed in its formation. Most commonly the organic moiety derived from an organic template is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular GeAPSO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the GeAPSO product and must be removed by calcining the GeAPSO at temperatures of 200° C. to 700° C., and preferably 350° C. to 600° C., to thermally degrade the organic species. In a few instances the pores of the GeAPSO product are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as are carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of the GeAPSO phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystalline process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula:

mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂

has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of germanium, aluminum, phosphorus and/or silicon, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized GeAPSO material.

Since the present GeAPSO compositions are formed from GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units which, respectively, have a net charge of 0, -1, +1 and 0, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO₂ ⁻ tetrahedra and charge-balancing cations. In the instant compositions, an AlO₂ ⁻ tetrahedron can be balanced electrically either by association with a PO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, a cation of germanium present in the reaction mixture, a proton (H⁺), or an organic cation derived from the templating agent. It has also been postulated that non-adjacent AlO₂ ⁻, and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺ and OH-respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971)].

The GeAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3Å in diameter. Ion exchange of GeAPSO compositions is ordinarily possible only after the organic moiety present as a result of synthesis has been removed from the pore system. Dehydration to remove water present in the as-synthesized GeAPSO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The GeAPSO materials will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.

In preparing the GeAPSO composition it is preferred to use a stainless steel reaction vessel lined with an inert plastic material, e.g., polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each GeAPSO composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the reagents admixed retain their identity in the intermediate mixture and in other cases some or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, it is preferred that the intermediate mixtures as well as the final reaction mixtures be stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis, using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2° (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2θ where θ is the Bragg angle as observed on the strip chart. Intensities were determined from the heights of diffraction peaks after subtracting background, "I_(o) " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks. Alternatively, the X-ray patterns may be obtained by use of computer based techniques using copper K-alpha radiation, Siemens type K-805 X-ray sources and Siemens D-500 X-ray powder diffractometers available from Siemens Corporation, Cherry Hill, N.J.

As will be understood by those skilled in the art, the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about ±0.4° on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak and very weak, respectively.

In certain instances hereinafter in the illustrative examples, the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.

The molecular sieves of the instant invention may be characterized by their X-ray powder diffraction patterns and such may have one of the X-ray patterns set forth in the following Tables A through W, wherein said X-ray patterns are for the as-synthesized form unless otherwise noted. In most cases, the pattern of the corresponding calcined form will also fall within the relevant table. However, in some cases the removal of the occluded templating agent which occurs during calcination will be accompanied by sufficient relaxation of the lattice to shift some of the lines slightly outside the ranges specified in the relevant table. In a small number of cases, calcination appears to cause more substantial distortion in the crystal lattice, and hence, more significant changes in the X-ray powder diffraction pattern.

                  TABLE A                                                          ______________________________________                                         (GeAPSO-5)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-7.7      12.28-11.48                                                                              m-vs                                                    19.4-19.9    4.58-4.46 w-m                                                     20.85-21.3   4.26-4.17 w-vs                                                    22.1-22.6    4.02-3.93 m-vs                                                    25.6-26.2    3.480-3.402                                                                              vw-m                                                    ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GeAPSO-11)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.8-8.2     11.19-10.85                                                                              m-s                                                      9.0-9.8     9.83-9.03 vw-vs                                                    19.9-20.5   4.46-4.33 m-s                                                      20.8-21.8   4.27-4.08 m-vs                                                     22.0-22.6   4.04-3.93 m-vs                                                     22.6-23.1   3.93-3.85 vw-vs                                                    23.1-23.5   3.85-3.79 w-vs                                                     ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GeAPSO-14)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                          8.6-8.9    10.3-9.93 vs                                                       13.0        6.81      w                                                        21.9-22.2   4.06-4.00 w                                                        25.4        3.51      w                                                        27.5        3.24      w                                                        29.7        3.01      w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GeAPSO-16)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         11.3-11.6    7.83-7.63 w-vs                                                    18.55-18.9   4.78-4.70 vw-m                                                    21.85-22.2   4.07-4.00 m-vs                                                    22.8-23.3    3.900-3.818                                                                              w-m                                                     26.4-27.3    3.370-3.267                                                                              w-m                                                     29.6-29.9    3.018-2.988                                                                              w-m                                                     ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GeAPSO-17)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.70-7.75    11.5-11.4 vs                                                      13.4         6.61      s-vs                                                     15.5-15.55  5.72-5.70 s                                                       19.65-19.7   4.52-4.51 w-s                                                     20.5-20.6    4.33-4.31 vs                                                      31.8-32.0    2.812-2.797                                                                              w-s                                                     ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GeAPSO-18)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                          9.6-9.65    9.21-9.16 vs                                                       15.5-15.55  5.72-5.70 m                                                       16.9-17.1    5.25-5.19 m                                                       20.15-20.25  4.41-4.39 m                                                       20.95-21.05  4.24-4.22 m                                                       31.8-32.5    2.814-2.755                                                                              m                                                       ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GeAPSO-20)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.8-14.2    6.42-6.23 m-vs                                                     19.6-20.15  4.53-4.41 m                                                       24.1-24.8    3.695-3.603                                                                              m-vs                                                    27.9-28.6    3.198-3.121                                                                              w                                                        31.3-32.05  2.861-2.791                                                                              w                                                       34.35-35.0   2.610-2.601                                                                              w-m                                                     ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GeAPSO-31)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.4-9.5     10.53-9.31                                                                               w-s                                                      20.2-20.4   4.40-4.35 m                                                        22.0-22.1   4.040-4.022                                                                              m                                                        22.5-22.7   3.952-3.92                                                                               vs                                                       31.6-31.8   2.831-2.814                                                                              w-m                                                      ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ      d(Å) Relative Intensity                                      ______________________________________                                         9.25-9.55     9.56-9.26                                                                               w-m                                                     12.5-12.9     7.08-6.86                                                                               vs                                                      16.9-17.3     5.25-5.13                                                                               w-m                                                     20.45-20.9    4.34-4.25                                                                               w-m                                                     23.85-24.25   3.73-3.67                                                                               w-m                                                     26.05-26.35   3.42-3.38                                                                               w-m                                                     27.3-27.6     3.27-3.23                                                                               vs                                                      ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ      d(Å) Relative Intensity                                      ______________________________________                                         13.15-13.4    6.73-6.61                                                                               vs                                                      18.05-18.35   4.91-4.83                                                                               m                                                       18.4-18.6     4.82-4.77                                                                               m                                                       26.55-26.7    3.36-3.34                                                                               m                                                       32.0-32.1     2.80-2.79                                                                               m                                                       ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GeAPSO-34)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.3-9.8      9.51-9.03 m-vs                                                    12.6-13.2    7.03-6.71 w-m                                                     15.8-16.3    5.61-5.44 vw-m                                                    20.25-21.2   4.39-4.19 w-vs                                                    24.8-25.4     3.59-3.507                                                                              vw-m                                                    30.0-30.9    2.979-2.894                                                                              vw-m                                                    ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GeAPSO-85)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.6-11.1    8.35-7.97 vw-vs                                                   13.1-13.7    6.76-6.46 vw-vs                                                   17.0-17.6    5.22-5.04 w-s                                                      20.6-21.25  4.31-4.18 vw-m                                                    21.6-22.3    4.11-3.99 m-vs                                                    28.1-28.8    3.175-3.100                                                                              vw-m                                                    ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GeAPSO-36)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.45-8.0     11.14-11.05                                                                              vs                                                      8.1-8.3      10.91-10.65                                                                              w-m                                                     16.3-16.6    5.44-5.34 w-m                                                     18.9-19.4    4.70-4.57 w-m                                                     20.7-21.0    4.29-4.23 w-m                                                     ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GeAPSO-37)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GeAPSO-39)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m                                                       13.1-13.5    6.76-6.56 m                                                       17.8-18.4    4.98-4.82 w-m                                                     20.8-21.3    4.27-4.17 m-vs                                                     22.2-22.85   4.00-3.892                                                                              m-vs                                                     26.4-27.05  3.376-3.296                                                                              w-m                                                     ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GeAPSO-40)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.5-7.7      11.79-11.48                                                                              vw-m                                                    8.0-8.1      11.05-10.94                                                                              s-vs                                                    12.4-12.5    7.14-7.08 w-vs                                                    13.6-13.8    6.51-6.42 m-s                                                     14.0-14.1    6.33-6.28 w-m                                                     27.8-28.0    3.209-3.187                                                                              w-m                                                     ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GeAPSO-41)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         13.6-13.8   6.51-6.42 w-m                                                      20.5-20.6   4.33-4.31 w-m                                                      21.1-21.3   4.21-4.17 vs                                                       22.1-22.3   4.02-3.99 m-s                                                      22.8-23.0   3.90-3.86 m                                                        23.1-23.4   3.82-3.80 w-m                                                      25.5-25.9   3.493-3.44                                                                               w-m                                                      ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GeAPSO-42)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.15-7.4     12.36-11.95                                                                              m-vs                                                     12.5-12.7   7.08-6.97 m-s                                                     21.75-21.9   4.09-4.06 m-s                                                      24.1-24.25  3.69-3.67 vs                                                      27.25-27.4   3.273-3.255                                                                              s                                                        30.05-30.25 2.974-2.955                                                                              m-s                                                     ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GeAPSO-43)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                          12.3-12.95  7.20-6.83 m-vs                                                     16.8-17.45  5.28-5.09 vw-w                                                    21.45-21.85  4.145-4.071                                                                              m-vs                                                     27.0-27.85  3.297-3.232                                                                              w-vs                                                    32.4-33.2    2.763-2.699                                                                              vw-m                                                    ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GeAPSO-44)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.2-9.6     9.61-9.21 m-vs                                                     15.9-16.3   5.57-5.44 vw-m                                                     20.5-21.0   4.33-4.23 m-vs                                                     24.3-25.1   3.66-3.548                                                                               w-m                                                      30.5-31.1   2.931-2.876                                                                              vw-m                                                     ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GeAPSO-46)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-8.1      12.28-10.92                                                                              vs                                                      12.9-13.6    6.86-6.51 vw                                                      21.2-22.2     4.19-4.501                                                                              vw-m                                                     22.5-23.45   3.95-3.793                                                                              vw-m                                                    26.6-27.9    3.351-3.198                                                                              vw-m                                                    ______________________________________                                    

                  TABLE W                                                          ______________________________________                                         (GeAPSO-47)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.4-9.6     9.41-9.21 vs                                                       12.8-13.1   6.92-6.76 vw-m                                                     16.0-16.3   5.54-5.44 vw-m                                                     20.5-21.0   4.31-4.23 m-vs                                                     24.6-25.3   3.613-3.526                                                                              vw-m                                                     30.6-31.1   2.921-2.876                                                                              vw-m                                                     ______________________________________                                    

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

Example 1 (Preparation of Al₂ O₃ /GeO₂ Precursor)

100 grams of 99.9% pure germanium tetrachloride (GeCl₄) were mixed with 676 grams of aluminum chlorhydrol (Al₂ Cl(OH)₅.2H₂ O). The composition of this mixture, expressed in terms of the molar oxide ratios of its components, was:

0.3 GeO₂ :1.0 Al₂ O₃

The resultant mixture was reduced in volume using a rotary evaporator until a thick gel was obtained, this gel was diluted with water and a solid mixture of oxides precipitated by slow addition of concentrated ammonium hydroxide until the pH reached approximately 8.0.

In order to remove all traces of the liquid phase, the oxide mixture was washed twice by centrifugation, filtered and washed free of chloride ion with a dilute ammonium hydroxide solution having a pH of approximately 8. The solid oxide mixture thus produced was dried at room temperature for several hours and finally dried at 100° C.

A sample of this solid oxide mixture was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             51.3                                                             GeO.sub.2     15.4                                                             Cl            3.3                                                              LOI*          32.0                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on a chloride-free basis in molar oxide ratios of:

0.29 GeO₂ :1.0 Al₂ O₃ :3.5 H₂ O

A portion of the solid oxide mixture thus produced was calcined at 350° C. for three hours. A sample of this solid oxide mixture was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             60.0                                                             GeO.sub.2     17.9                                                             Cl            2.8                                                              LOI*          20.5                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on a chloride-free basis, in molar oxide ratios of:

0.29 GeO₂ :1.0 Al₂ O₃ :1.9 H₂ O

Example 2 (Preparation of Al₂ O₃ /SiO₂ /GeO₂ Precursor)

12.6 grams of germanium ethoxide (Ge(OC₂ H₅)₄ were mixed with 10.4 grams of tetraethyl orthosilicate, and then there were mixed in 98.5 grams of aluminum tri-sec-butoxide (Al(OC₄ H₉)₃). To the resultant mixture were added 14.4 grams of water, and the resultant mixture was blended using a mechanical mixer. To ensure complete hydrolysis of the alkoxides, an additional 40.0 grams of water were added and the resultant mixture was dried at 100° C. for several hours. To the dried solids were added 20.0 grams of water, and the resultant slurry was dried at 100° C. overnight.

A sample of the resultant solid oxide mixture was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             41.2                                                             GeO.sub.2     10.2                                                             SiO.sub.2     8.8                                                              LOI*          38.2                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition in molar oxide ratios of:

0.24 GeO₂ :1.00 Al₂ O₃ :0.36 SiO₂ :5.25 H₂ O.

Example 3 (Preparation of GeAPSO-5)

(a) GeAPSO-5 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 TPA:0.05-0.2 GeO₂ :0.5-1.0 Al₂ O₃ :

0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂ :40-100 H₂ O

where "TPA" denotes tripropylamine.

The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce GeAPSO-5 product. Solids are recovered by filtration, washed with water and dried in air at room temperature.

The GeAPSO-5 product's chemical analysis shows the GeAPSO-5 product contains germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of a GeAPSO-5 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-7.7      12.28-11.48                                                                              m-vs                                                    19.4-19.9    4.58-4.46 w-m                                                     20.85-21.3   4.26-4.17 w-vs                                                    22.1-22.6    4.02-3.93 m-vs                                                    25.6-26.2    3.480-3.402                                                                              vw-m                                                    ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined GeAPSO-5 is also characterized by the X-ray pattern of part (a).

(c) When the calcined GeAPSO-5 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter (Å)                                                                          (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    7                                         O.sub.2  3.46       750      -183    10                                        Neopentane                                                                              6.2        700      24      4                                         H.sub.2 O                                                                               2.65       4.3      24      4                                         H.sub.2 O                                                                               2.65       20.0     24      12                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GeAPSO-5 is greater than 6.2 Å.

Example 4 (Preparation of GeAPSO-11)

A mixture was formed by combining 23.1 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 50.4 grams of water and 5.4 grams of diethanolamine (DEA) and adding to the resultant solution 13.6 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O. To this mixture were added 20.2 grams of di-n-propylamine (DPA), and the resultant mixture was stirred with a magnetic stirrer until homogeneous. This homogeneous mixture was combined with a solution consisting of 4.2 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) and 10.1 grams of germanium ethoxide (Ge(OC₂ H₅)₄) and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

2.0 DPA:0.5 DEA:0.38 GeO₂ :1.00 Al₂ O₃ :

0.20 SiO₂ :1.00 P₂ O₅ :30.0 H₂ O.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 72 hours. The solid reaction product (which was determined by the analyses described below to be mainly GeAPSO-11) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        4.4                                                              Nitrogen      0.91                                                             GeO.sub.2     4.6                                                              Al.sub.2 O.sub.3                                                                             42.5                                                             SiO.sub.2     5.2                                                              P.sub.2 O.sub.5                                                                              34.0                                                             LOI*          12.1                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on an anhydrous basis, in molar oxide ratios of:

0.15 DPA:0.11 GeO₂ :1.0 Al₂ O₃ :

0.21 SiO₂ :0.57 P₂ O₅

which corresponds to an empirical chemical formula, on an anhydrous basis, of:

0.04 DPA:(Ge₀.03 Al₀.58 P₀.33 Si₀.06)O₂

so that the product contained germanium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GeAPSO-11. Electron microprobe spot analysis of a clean one of these crystals indicated the following approximate composition:

Ge₀.03 Al₀.45 P₀.46 Si₀.05

thus indicating that the product contained germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the major product, as synthesized, was characterized by the data in the following Table BA:

                  TABLE BA                                                         ______________________________________                                         (GeAPSO-11)                                                                                         Relative Intensity                                        2θ     d(Å)                                                                               100 × I/I.sub.ο                             ______________________________________                                          8.2         10.82   16.1                                                       9.5         9.28    100                                                       15.8         5.623   36.1                                                      19.1         4.652   8.4                                                       20.5         4.334   12.8                                                      21.1         4.206   35.7                                                      22.2         3.997   31.8                                                      22.8         3.895   37.7                                                      23.3         3.819   50.9                                                      24.8         3.586   8.6                                                       28.8         3.102   20.9                                                      33.0         2.716   6.8                                                       34.4         2.610   7.4                                                       38.0         2.371   7.5                                                       ______________________________________                                    

Example 5 (Preparation of GeAPSO-17)

(a) GeAPSO-17 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 QN:0.05-0.2 GeO₂ :0.5-1.0 Al₂ O₃ :

0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂ :40-100 H₂ O

where "QN" denotes quinuclidine.

The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce GeAPSO-17 product. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GeAPSO-17 product's chemical analysis shows the GeAPSO-17 product contains germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of a GeAPSO-17 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.70-7.75    11.5-11.4 vs                                                      13.4         6.61      s-vs                                                     15.5-15.55  5.72-5.70 s                                                       19.65-19.7   4.52-4.51 w-s                                                     20.5-20.6    4.33-4.31 vs                                                      31.8-32.0    2.812-2.797                                                                              w-s                                                     ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined GeAPSO-17 is also characterized by the X-ray pattern of part (a).

(c) When the calcined GeAPSO-17 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    10                                        O.sub.2  3.46       750      -183    12                                        n-Butane 4.3        100      24       4                                        H.sub.2 O                                                                               2.65       4.3      24      13                                        H.sub.2 O                                                                               2.65        20      24      14                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GeAPSO-17 is about 4.3 Å.

Example 6 (Preparation of GeAPSO-31)

(a) GeAPSO-31 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 DPA:0.05-0.2 GeO₂ :0.5-1.0 Al₂ O₃ :

0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂ :40-100 H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is seeded with crystals of AlPO₄ -31 (U.S. Pat. No. 4,310,440) and digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce GeAPSO-31 product. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GeAPSO-31 product's chemical analysis shows the GeAPSO-31 product contains germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of a GeAPSO-31 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å)  Relative Intensity                                      ______________________________________                                         8.4-9.5      10.53-9.31                                                                               w-s                                                     20.2-20.4    4.40-4.35 m                                                       22.0-22.1    4.040-4.022                                                                              m                                                       22.5-22.7    3.952-3.92                                                                               vs                                                      31.6-31.8    2.831-2.814                                                                              w-m                                                     ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined GeAPSO-31 is also characterized by the X-ray pattern of part (a).

(c) When the calcined GeAPSO-31 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    4                                         O.sub.2  3.46       750      -183    6                                         Cyclohexane                                                                             6.0         90      24      3                                         Neopentane                                                                              6.2        700      24      3                                         H.sub.2 O                                                                               2.65       4.3      24      3                                         H.sub.2 O                                                                               2.65        20      24      10                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GeAPSO-31 is greater than about 6.2 Å.

Example 7 (Preparation of GeAPSO-34)

A solution was formed by combining 23.1 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 73.5 grams of 40 percent aqueous tetraethylammonium hydroxide (TEAOH). A second solution was prepared from 4.2 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) and 10.1 grams of germanium ethoxide (Ge(OC₂ H₅)₄). The two solutions were combined, blended until homogeneous and then added to 13.6 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O, and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

2.0 TEAOH:0.4 GeO₂ :1.00 Al₂ O₃ :

0.2 SiO₂ :1.00 P₂ O₅ :30.0 H₂ O:2.4 C₂ H₅ OH.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 120 hours. The solid reaction product (which was determined by the analyses described below to be mainly GeAPSO-34) was recovered by centrifugation, washed thoroughly with water and dried in air at ambient temperature and then at 100° C. overnight.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        9.9                                                              Nitrogen      1.4                                                              GeO.sub.2     5.4                                                              Al.sub.2 O.sub.3                                                                             34.0                                                             SiO.sub.2     2.7                                                              P.sub.2 O.sub.5                                                                              41.8                                                             LOI*          17.2                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on an anhydrous basis, in molar oxide ratios of:

0.31 TEAOH:0.15 GeO₂ :1.0 Al₂ O₃ :

0.13 SiO₂ :0.88 P₂ O₅

which corresponds to an empirical chemical formula, on an anhydrous basis, of:

0.08 TEAOH:(Ge₀.04 Al₀.49 P₀.44 Si₀.03)O₂

so that the product contained germanium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GeAPSO-34. Electron microprobe spot analysis of a clean one of these crystals indicated the following approximate composition:

Ge₀.07 Al₀.43 P₀.44 Si₀.06

thus indicating that the product contained germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the major product, as synthesized, was characterized by the data in the following Table LA:

                  TABLE LA                                                         ______________________________________                                         (GeAPSO-34)                                                                                        Relative Intensity                                         2θ     d(Å)                                                                              100 × I/I.sub.ο                              ______________________________________                                          9.5         9.28   100                                                        12.9         6.89   14.8                                                       14.1         6.28   15.3                                                       16.0         5.53   45.7                                                       18.0         4.92   26.4                                                       20.6         4.31   82.9                                                       25.3         3.58   27.6                                                       25.9         3.45   16.1                                                       30.6         2.93   29.7                                                       31.3         2.86   21.1                                                       ______________________________________                                    

A sample of the GeAPSO-34 produced above was calcined in air at 600° C. for 3 hours and was then utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated at 350° C. in a vacuum for 16 hours. The following data were generated in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter (Å)                                                                          (Torr)   Temp, °C.                                                                       Adsorbed                                  ______________________________________                                         O.sub.2  3.46       100      -183    24.7                                      Neopentane                                                                              6.2        700      23      2.0                                       n-Hexane 4.3         45      22      11.5                                      n-Butane 4.3        700      22      14.1                                      iso-Butane                                                                              5.0        700      22      0.2                                       H.sub.2 O                                                                               2.65       4.6      22      29.8                                      ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater that about 4.3 Å, as shown by the adsorption of n-hexane and n-butane (kinetic diameters of 4.3 Å), but less than about 5.0 Å, as shown by the negligible adsorption of iso-butane (kinetic diameter of 5.0 Å).

Example 8 (Preparation of GeAPSO-34)

A solution was formed by combining 23.1 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 19.1 grams of water. To this solution were added 13.6 grams of hydrated aluminum oxide in the form of a pseudoboehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O. The resultant mixture was combined with a second solution prepared by adding 4.2 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) to 10.1 grams of germanium ethoxide (Ge(OC₂ H₅)₄) and the resultant mixture stirred briefly. To the resultant mixture were added 73.5 grams of 40 wt. percent aqueous tetraethylammonium hydroxide (TEAOH) and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

2.0 TEAOH:0.4 GeO₂ :1.00 Al₂ O₃ :0.20 SiO₂ :

1.00 P₂ O₅ :30.0 H₂ O:2.4 C₂ H₅ OH

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 120 hours. The solid reaction product (which was determined by the analyses described below to be mainly GeAPSO-34) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        10.2                                                             Nitrogen      1.4                                                              GeO.sub.2     3.5                                                              Al.sub.2 O.sub.3                                                                             33.0                                                             SiO.sub.2     5.4                                                              P.sub.2 O.sub.5                                                                              40.7                                                             LOI*          17.0                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on an anhydrous basis, in molar oxide ratios of:

0.33 TEAOH:0.10 GeO₂ :1.00 Al₂ O₃ :

0.28 SiO₂ :0.89 P₂ O₅

which corresponds to an empirical chemical formula, on an anhydrous basis, of:

0.08 TEAOH:(Ge₀.02 Al₀.48 P₀.43 Si₀.07)O₂

so that the product contained germanium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GeAPSO-34. Electron microprobe spot analysis of a clean one of these crystals indicated the following approximate composition:

Ge₀.04 Al₀.44 P₀.40 Si₀.12

thus indicating that the product contained germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the major product, as synthesized, was essentially identical to that set forth in Table LA above.

Example 9 (Preparation of GeAPSO-34)

A solution was formed by combining 10.13 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄ ) with 8.9 grams of water and 32.2 grams of 40 wt. percent aqueous tetraethylammonium hydroxide (TEAOH). To this solution were added 8.7 grams of the solid oxide mixture prepared in Example 2 above, and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

2.5 TEAOH:0.24 GeO₂ :1.00 Al₂ O₃ :

0.36 SiO₂ :1.25 P₂ O₅ :56.2 H₂ O.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 72 hours. The solid reaction product (which was determined by the analyses described below to be mainly GeAPSO-34) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        11.8                                                             Nitrogen      1.8                                                              GeO.sub.2     0.86                                                             Al.sub.2 O.sub.3                                                                             32.8                                                             SiO.sub.2     7.2                                                              P.sub.2 O.sub.5                                                                              41.2                                                             LOI*          19.1                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on an anhydrous basis, in molar oxide ratios of:

0.38 TEAOH:0.025 GeO₂ : 1.00 Al₂ O₃ :

0.37 SiO₂ :0.90 P₂ O₅

which corresponds to an empirical chemical formula, on an anhydrous basis, of:

0.09 TEAOH:(Ge₀.01 Al₀.48 P₀.43 Si₀.09)O₂

so that the product contained germanium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GeAPSO-34. Electron microprobe spot analysis of a clean one of these crystals indicated the following approximate composition:

Ge₀.07 Al₀.45 P₀.33 Si₀.15

thus indicating that the product contained germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the major product, as synthesized, was essentially identical to that set forth in Table LA above.

Example 10 (Preparation of GeAPSO-34)

A solution was formed by combining 8.9 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) with 15.2 grams of water, 7.1 grams of 40 wt. percent aqueous tetraethylammonium hydroxide (TEAOH) and 7.9 grams of di-n-propylamine (DPA). To this solution were added 5.3 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O and the resultant mixture was blended thoroughly until homogeneous. The resultant mixture was then combined with a second solution prepared by blending 1.6 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) with 3.9 grams of germanium ethoxide (Ge(OC₂ H₅)₄) and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

0.5 TEAOH:2.0 DPA:0.4 GeO₂ :1.00 Al₂ O₃ :

0.2 SiO₂ :1.0 P₂ O₅ :30.0 H₂ O:2.4 C₂ H₅ OH.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 72 hours. The solid reaction product (which was determined by X-ray powder diffraction analysis to be mainly GeAPSO-34) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

The X-ray powder diffraction pattern of the major product, as synthesized, was essentially identical to that set forth in Table LA above.

Example 11 (Preparation of GeAPSO-34)

A solution was formed by combining 9.3 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄ ) with 15.2 grams of water and 7.4 grams of 40 wt. percent aqueous tetraethylammonium hydroxide (TEAOH). With this solution were mixed 6.5 grams of the solid oxide mixture prepared in Example 1 above. To the resultant mixture were added 8.2 grams of di-n-propylamine (DPA), and the resultant mixture was stirred until homogeneous. To this mixture. The resultant mixture was then combined with 2.5 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) with stirring. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

0.63 TEAOH:2.48 DPA:0.29 GeO₂ :1.00 Al₂ O₃ :

0.37 SiO₂ :1.23 P₂ O₅ :43 H₂ O:1.5 C₂ H₅ OH.

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 72 hours. The solid reaction product (which was determined by X-ray powder diffraction analysis to be mainly GeAPSO-34) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

The X-ray powder diffraction pattern of the major product, as synthesized, was essentially identical to that set forth in Table LA above.

The as-synthesized specimens of GeAPSO-34 prepared in Examples 7-11 above, all had similar X-ray powder diffraction patterns. The following general Table LB summarizes the X-ray powder diffraction lines which were obtained from the various as-synthesized specimens of GeAPSO-34; the least intense lines were not obtained from every specimen.

                  TABLE LB                                                         ______________________________________                                         (GeAPSO-34)                                                                                          Relative Intensity                                       2θ     d(Å) 100 × I/I.sub.ο                            ______________________________________                                         9.5-9.6      9.23-9.28                                                                               100                                                      12.9         6.86-6.89                                                                               12.5-16.3                                                14.1-14.2    6.26-6.28                                                                               11.5-15.3                                                16.0-16.1    5.51-5.53                                                                               45.7-47.5                                                18.0-18.1    4.91-4.92                                                                               16.7-26.4                                                20.6         4.30-4.31                                                                               76.9-88.6                                                25.3         3.52-3.58                                                                               18.8-27.6                                                25.9         3.44-3.45                                                                               16.0-19.1                                                30.6         2.92-2.93                                                                               26.7-32.2                                                31.3         2.86     19.1-23.0                                                ______________________________________                                    

Example 12 (Preparation of GeAPSO-44)

(a) GeAPSO-44 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:

1.0-2.0 CHA:0.05-0.2 GeO₂ :0.5-1.0 Al₂ O₃ :

0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂ :40-100 H₂ O

where "CHA" denotes cyclohexylamine.

The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce GeAPSO-44 product. Solids are then recovered by filtration, washed with water and dried in air at room temperature.

The GeAPSO-44 product's chemical analysis shows the GeAPSO-44 product contains germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of a GeAPSO-44 product is characterized by the following data:

    ______________________________________                                         2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m-vs                                                    15.9-16.3    5.57-5.44 vw-m                                                    20.5-21.0    4.33-4.23 m-vs                                                    24.3-25.1     3.66-3.548                                                                              w-m                                                     30.5-31.1    2.931-2.876                                                                              vw-m                                                    ______________________________________                                    

(b) When the calcined GeAPSO-44 is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350° C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter(Å)                                                                           (Torr)   Temp, °C.                                                                       Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       100      -183    13                                        O.sub.2  3.46       750      -183    16                                        n-Hexane 4.3        100      24      2                                         H.sub.2 O                                                                               2.65       4.3      24      15                                        H.sub.2 O                                                                               2.65        20      24      17                                        ______________________________________                                          *typical amount adsorbed                                                 

The pore diameter of GeAPSO-44 is about 4.3Å.

Example 13 (Preparation of GeAPSO-35)

A solution was formed by combining 23.1 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄ ) with 19.2 grams of water. To this solution were added 13.6 grams of hydrated aluminum oxide in the form of a pseudoboehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O. The resultant mixture was combined with a second solution prepared by adding 4.2 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) to 10.1 grams of germanium ethoxide (Ge(OC₂ H₅)₄) and the resultant mixture was blended thoroughly with a spatula until homogeneous. To the resultant mixture was added a solution of 44.5 grams of quinuclidine (QN) in 24.0 grams of water, and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

4.0 QN:0.4 GeO₂ :1.00 Al₂ O₃ :0.20 SiO₂ :

1.00 P₂ O₅ :30.0 H₂ O:2.4 C₂ H₅ OH

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200° C. under autogenous pressure for 24 hours. The solid reaction product (which was determined by the analyses described below to be mainly GeAPSO-35) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

A sample of this solid reaction product was analyzed and the following chemical analysis obtained:

    ______________________________________                                         Component     Weight percent                                                   ______________________________________                                         Carbon        28.9                                                             Nitrogen      4.6                                                              GeO.sub.2     8.4                                                              Al.sub.2 O.sub.3                                                                             23.3                                                             SiO.sub.2     2.8                                                              P.sub.2 O.sub.5                                                                              23.2                                                             LOI*          42.9                                                             ______________________________________                                          *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition, on an anhydrous basis, in molar oxide ratios of:

1.5 QN:0.35 GeO₂ :1.00 Al₂ O₃ :

0.20 SiO₂ :0.72 P₂ O₅

which corresponds to an empirical chemical formula, on an anhydrous basis, of:

0.38 QN:(Ge₀.09 Al₀.50 P₀.36 Si₀.05)O₂

so that the product contained germanium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

Scanning electron microscopy of the solid product showed numerous crystals with a morphology corresponding to that expected for GeAPSO-35. Electron microprobe spot analysis of a clean one of these crystals indicated the following approximate composition:

Ge₀.07 Al₀.44 P₀.33 Si₀.09

thus indicating that the product contained germanium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the major product, as synthesized, was characterized by the data in the following Table MA:

                  TABLE MA                                                         ______________________________________                                         (GeAPSO-35)                                                                                        Relative Intensity                                         2θ     d(Å)                                                                              100 × I/I.sub.ο                              ______________________________________                                          8.7         10.2   19.7                                                       11.0         8.03   45.1                                                       13.4         6.63   26.5                                                       15.9         5.57   9.3                                                        17.3         5.12   73.1                                                       17.8         4.97   13.8                                                       21.2         4.19   42.3                                                       21.9         4.06   100.0                                                      26.8         3.32   21.2                                                       28.5         3.13   22.1                                                       28.8         3.10   18.6                                                       32.1         2.79   42.8                                                       34.9         2.59   8.1                                                        ______________________________________                                    

A sample of the GeAPSO-35 produced above was calcined in air at 600° C. for 3 hours and then utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated at 350° C. in a vacuum for 16 hours. The following data were generated in the adsorption studies:

    ______________________________________                                                  Kinetic    Pressure         Wt. %                                     Adsorbate                                                                               Diameter (Å)                                                                          (Torr)   Temp, °C.                                                                       Adsorbed                                  ______________________________________                                         O.sub.2   3.46      100      -183    15.7                                      Neopentane                                                                              6.2        700      23      3.1                                       n-Hexane 4.3         45      22      8.5                                       n-Butane 4.3        700      22      3.2                                       iso-Butane                                                                              5.0        700      22      1.4                                       H.sub.2 O                                                                                2.65      4.6      22      21.3                                      ______________________________________                                    

From the above data, the pore size of the calcined product was determined to be greater than about 4.3 Å, as shown by the adsorption of n-hexane and n-butane (kinetic diameters of 4.3 Å), but less than about 5.0 Å, as shown by the low adsorption of iso-butane (kinetic diameter of 5.0 Å). Although some adsorption of neopentane was recorded, the structure type to which GeAPSO-35 belongs is known to have pore diameters less than 6.2 Å.

Example 14 (Preparation of GeAPSO-43)

A solution was formed by combining 9.8 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄ ) with 10.0 grams of water. To this solution were added 5.8 grams of hydrated aluminum oxide in the form of a pseudoboehmite phase comprising 75.1 wt. percent of Al₂ O₃ and 24.9 wt. percent of H₂ O. The resultant mixture was combined with a second solution prepared by adding 1.8 grams of tetraethyl orthosilicate (Si(OC₂ H₅)₄) to 4.3 grams of germanium ethoxide (Ge(OC₂ H₅)₄) and the resultant mixture was mixed briefly. To the resultant mixture was added 30.7 grams of tetramethylammonium hydroxide pentahydrate (TMAOH.5H₂ O), and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:

4.0 TMAOH:0.38 GeO₂ :1.00 Al₂ O₃ :

0.20 SiO₂ :1.00 P₂ O₅ :30.0 H₂ O

This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150° C. under autogenous pressure for 72 hours. The solid reaction product (which was determined by the X-ray analysis described below to be mainly GeAPSO-43) was recovered by centrifugation, washed with water and dried in air at ambient temperature and then at 100° C. overnight.

The X-ray powder diffraction pattern of the major product, as synthesized, was characterized by the data in the following Table TA:

                  TABLE TA                                                         ______________________________________                                         (GeAPSO-43)                                                                                        Relative Intensity                                         2θ     d(Å)                                                                              100 × I/I.sub.ο                              ______________________________________                                         12.4         7.133  100                                                        16.9         5.249  6.2                                                        21.0         4.238  31.8                                                       21.8         4.084  83.5                                                       23.9         3.722  4.6                                                        27.0         3.304  96.5                                                       28.6         3.120  21.0                                                       32.5         2.756  30.1                                                       44.9         2.016  10.2                                                       ______________________________________                                    

The GeAPSO compositions of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefins and aromatic species, e.g., benzene, xylenes and cumene. Thus the present molecular sieve compositions as a class are useful as desiccants in such adsorption separation/purification processes as natural gas drying, cracked gas drying. Water is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen. These GeAPSOs are therefore suitably employed in the drying of reformer hydrogen streams and in the drying of oxygen, nitrogen or air prior to liquefaction.

The present GeAPSO compositions also exhibit novel surface selectivity characteristics which render them useful as catalyst or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art (for example ion exchange) and used, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4A are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by GeAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.

Using GeAPSO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400° F. to 825° F. (204° C. to 441° C.) using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g. (0.171 to 24.23 MPa.), and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.

The GeAPSO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700° F. to 1000° F. (371° C. to 538° C.), hydrogen pressures of from 100 to 500 p.s.i.g. (0.791 to 3.448 MPa.), LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerization processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200°πF. to 600° F. (93° C. to 316° C.), preferably 300° F. to 550° F. (149° C. to 288° C.) with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixture with the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F. (343° C. to 538° C.), preferably 850° F. to 950° F. (454° C. to 510° C.) and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g. (205 to 446 KPa.), the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C₇ -C₂₀. Contact time between the feedstock and the catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.

The unique crystal structure of the present GeAPSO catalysts and their availability in a form totally void of alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition. Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400° to 750° F. (204° to 399° C.), pressures in the range of 100 to 2000 p.s.i.g. (0.791 to 13.89 MPa.) and LHSV values in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with GeAPSO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850° to 1100° F. (454° to 593° C.), LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. (101 to 446 KPa.) are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the GeAPSO catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.

In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800°-1000° F. (427°-538° C.) are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g. (2.17-6.895 MPa.), other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like. Any of these may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than with a feed containing less organonitrogen compounds. Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks, in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500°-900° F. (260°-482° C.), while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700°-1000° F. (371°-538° C.). Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexane to isohexene, cyclohexene to methylcyclopentane etc. The preferred form of the catalyst is a combination of the GeAPSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the GeAPSO compositions having pores of at least 5 Å are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350° F. (177° C.) and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700° F. (371° C.). The temperature is preferably at least 450° F. (232° C.) and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low as 250° F. (121° C.) but is preferably at least 350° F. (177° C.). In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene. 

We claim:
 1. Crystalline molecular sieves comprising three-dimensional microporous framework structures of GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂ wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to H and J to W

                  TABLE A                                                          ______________________________________                                         (GeAPSO-5)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-7.7      12.28-11.48                                                                              m-vs                                                    19.4-19.9    4.58-4.46 w-m                                                     20.85-21.3   4.26-4.17 w-vs                                                    22.1-22.6    4.02-3.93 m-vs                                                    25.6-26.2    3.480-3.402                                                                              vw-m                                                    ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GeAPSO-11)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.8-8.2     11.19-10.85                                                                              m-s                                                      9.0-9.8     9.83-9.03 vw-vs                                                    19.9-20.5   4.46-4.33 m-s                                                      20.8-21.8   4.27-4.08 m-vs                                                     22.0-22.6   4.04-3.93 m-vs                                                     22.6-23.1   3.93-3.85 vw-vs                                                    23.1-23.5   3.85-3.79 w-vs                                                     ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GeAPSO-14)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.6-8.9     10.3-9.93 vs                                                       13.0        6.81      w                                                        21.9-22.2   4.06-4.00 w                                                        25.4        3.51      w                                                        27.5        3.24      w                                                        29.7        3.01      w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GeAPSO-16)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         11.3-11.6   7.83-7.63 w-vs                                                     18.55-18.9  4.78-4.70 vw-m                                                     21.85-22.2  4.07-4.00 m-vs                                                     22.8-23.3   3.900-3.818                                                                              w-m                                                      26.4-27.3   3.370-3.267                                                                              w-m                                                      29.6-29.9   3.018-2.988                                                                              w-m                                                      ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GeAPSO-17)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.70-7.75   11.5-11.4 vs                                                       13.4        6.61      s-vs                                                      15.5-15.55 5.72-5.70 s                                                        19.65-19.7  4.52-4.51 w-s                                                      20.5-20.6   4.33-4.31 vs                                                       31.8-32.0   2.812-2.797                                                                              w-s                                                      ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GeAPSO-18)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                          9.6-9.65   9.21-9.16 vs                                                        15.5-15.55 5.72-5.70 m                                                        16.9-17.1   5.25-5.19 m                                                        20.15-20.25 4.41-4.39 m                                                        20.95-21.05 4.24-4.22 m                                                        31.8-32.5   2.814-2.755                                                                              m                                                        ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GeAPSO-20)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         13.8-14.2   6.42-6.23 m-vs                                                      19.6-20.15 4.53-4.41 m                                                        24.1-24.8   3.695-3.603                                                                              m-vs                                                     27.9-28.6   3.198-3.121                                                                              w                                                         31.3-32.05 2.861-2.791                                                                              w                                                        34.35-35.0  2.610-2.601                                                                              w-m                                                      ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GeAPSO-31)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.4-9.5     10.53-9.31                                                                               w-s                                                      20.2-20.4   4.40-4.35 m                                                        22.0-22.1   4.040-4.022                                                                              m                                                        22.5-22.7   3.952-3.92                                                                               vs                                                       31.6-31.8   2.831-2.814                                                                              w-m                                                      ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         9.25-9.55    9.56-9.26                                                                               w-m                                                      12.5-12.9    7.08-6.86                                                                               vs                                                       16.9-17.3    5.25-5.13                                                                               w-m                                                      20.45-20.9   4.34-4.25                                                                               w-m                                                      23.85-24.25  3.73-3.67                                                                               w-m                                                      26.05-26.35  3.42-3.38                                                                               w-m                                                      27.3-27.6    3.27-3.23                                                                               vs                                                       ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         13.15-13.4   6.73-6.61                                                                               vs                                                       18.05-18.35  4.91-4.83                                                                               m                                                        18.4-18.6    4.82-4.77                                                                               m                                                        26.55-26.7   3.36-3.34                                                                               m                                                        32.0-32.1    2.80-2.79                                                                               m                                                        ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GeAPSO-34)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.3-9.8     9.51-9.03 m-vs                                                     12.6-13.2   7.03-6.71 w-m                                                      15.8-16.3   5.61-5.44 vw-m                                                     20.25-21.2  4.39-4.19 w-vs                                                     24.8-25.4    3.59-3.507                                                                              vw-m                                                     30.0-30.9   2.979-2.894                                                                              vw-m                                                     ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GeAPSO-35)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.6-11.1    8.35-7.97 vw-vs                                                   13.1-13.7    6.76-6.46 vw-vs                                                   17.0-17.6    5.22-5.04 w-s                                                      20.6-21.25  4.31-4.18 vw-m                                                    21.6-22.3    4.11-3.99 m-vs                                                    28.1-28.8    3.175-3.100                                                                              vw-m                                                    ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GeAPSO-36)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.45-8.0    11.14-11.05                                                                              vs                                                       8.1-8.3     10.91-10.65                                                                              w-m                                                      16.3-16.6   5.44-5.34 w-m                                                      18.9-19.4   4.70-4.57 w-m                                                      20.7-21.0   4.29-4.23 w-m                                                      ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GeAPSO-37)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GeAPSO-39)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m                                                       13.1-13.5    6.76-6.56 m                                                       17.8-18.4    4.98-4.82 w-m                                                     20.8-21.3    4.27-4.17 m-vs                                                     22.2-22.85   4.00-3.892                                                                              m-vs                                                     26.4-27.05  3.376-3.296                                                                              w-m                                                     ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GeAPSO-40)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.5-7.7      11.79-11.48                                                                              vw-m                                                    8.0-8.1      11.05-10.94                                                                              s-vs                                                    12.4-12.5    7.14-7.08 w-vs                                                    13.6-13.8    6.51-6.42 m-s                                                     14.0-14.1    6.33-6.28 w-m                                                     27.8-28.0    3.209-3.187                                                                              w-m                                                     ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GeAPSO-41)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.6-13.8    6.51-6.42 w-m                                                     20.5-20.6    4.33-4.31 w-m                                                     21.1-21.3    4.21-4.17 vs                                                      22.1-22.3    4.02-3.99 m-s                                                     22.8-23.0    3.90-3.86 m                                                       23.1-23.4    3.82-3.80 w-m                                                     25.5-25.9    3.493-3.44                                                                               w-m                                                     ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GeAPSO-42)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.15-7.4     12.36-11.95                                                                               m-vs                                                   12.5-12.7    7.08-6.97 m-s                                                     21.75-21.9   4.09-4.06 m-s                                                      24.1-24.25  3.69-3.67 vs                                                      27.25-27.4   3.273-3.255                                                                              s                                                       30.05-30.25  2.974-2.955                                                                              m-s                                                     ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GeAPSO-43)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         12.3-12.95   7.20-6.83 m-vs                                                    16.8-17.45   5.28-5.09 vw-w                                                    21.45-21.85  4.145-4.071                                                                              m-vs                                                    27.0-27.85   3.297-3.232                                                                              w-vs                                                    32.4-33.2    2.763-2.699                                                                              vw-m                                                    ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GeAPSO-44)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m-vs                                                    15.9-16.3    5.57-5.44 vw-m                                                    20.5-21.0    4.33-4.23 m-vs                                                    24.3-25.1    3.66-3.548                                                                               w-m                                                     30.5-31.1    2.931-2.876                                                                              vw-m                                                    ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GeAPSO-46)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-8.1      12.28-10.92                                                                              vs                                                      12.9-13.6    6.86-6.51 vw                                                      21.2-22.2     4.19-4.501                                                                              vw-m                                                     22.5-23.45   3.95-3.793                                                                              vw-m                                                    26.6-27.9    3.351-3.198                                                                              vw-m                                                    ______________________________________                                    

                  TABLE W                                                          ______________________________________                                         (GeAPSO-47)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4-9.6      9.41-9.21 vs                                                      12.8-13.1    6.92-6.76 vw-m                                                    16.0-16.3    5.54-5.44 vw-m                                                    20.5-21.0    4.31-4.23 m-vs                                                    24.6-25.3    3.613-3.526                                                                              vw-m                                                    30.6-31.1    2.921-2.876                                                                              vw-m.                                                   ______________________________________                                    


2. Crystalline molecular sieves according to claim 1 wherein the mole fractions of germanium, aluminum, phosphorus and silicon present as tetrahedral oxides are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG.
 2. 3. Crystalline molecular sieves according to claim 2 wherein the mole fractions of germanium, aluminum, phosphorus and silicon present as tetrahedral oxides are within the hexagonal compositional area defined by points g, h, i, j, k and l of FIG.
 2. 4. The crystalline molecular sieves according to claim 1 or claim 2 wherein "m" is not greater than about 0.15.
 5. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table A given in claim
 1. 6. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table B given in claim
 1. 7. The crystalline molecular sieves of claim 6 wherein the X-ray powder diffraction pattern set forth in Table B contains at least the d-spacings set forth in the following Table BA:

                  TABLE BA                                                         ______________________________________                                         (GeAPSO-11)                                                                                         Relative Intensity                                        2θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                         8.2          10.82   16.1                                                      9.5          9.28    100                                                       15.8         5.623   36.1                                                      19.1         4.652   8.4                                                       20.5         4.334   12.8                                                      21.1         4.206   35.7                                                      22.2         3.997   31.8                                                      22.8         3.895   37.7                                                      23.3         3.819   50.9                                                      24.8         3.586   8.6                                                       28.8         3.102   20.9                                                      33.0         2.716   6.8                                                       34.4         2.610   7.4                                                       38.0         2.371   7.5                                                       ______________________________________                                    


8. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table C given in claim
 1. 9. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table D given in claim
 1. 10. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table E given in claim
 1. 11. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table F given in claim
 1. 12. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table G given in claim
 1. 13. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table H given in claim
 1. 14. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table J given in claim
 1. 15. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table K given in claim
 1. 16. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table L given in claim
 1. 17. The crystalline molecular sieves of claim 16 wherein the X-ray powder diffraction pattern set forth in Table L contains at least the d-spacings set forth in the following Table LA:

                  TABLE LA                                                         ______________________________________                                         (GeAPSO-34)                                                                                         Relative Intensity                                        2θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                          9.5         9.28    100                                                       12.9         6.89    14.8                                                      14.1         6.28    15.3                                                      16.0         5.53    45.7                                                      18.0         4.92    26.4                                                      20.6         4.31    82.9                                                      25.3         3.58    27.6                                                      25.9         3.45    16.1                                                      30.6         2.93    29.7                                                      31.3         2.86    21.1.                                                     ______________________________________                                    


18. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table M given in claim
 1. 19. The crystalline molecular sieves of claim 18 wherein the X-ray powder diffraction pattern set forth in Table M contains at least the d-spacings set forth in the following Table MA:

                  TABLE MA                                                         ______________________________________                                         (GeAPSO-35)                                                                                         Relative Intensity                                        2θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                         8.7          10.2    19.7                                                      11.0         8.03    45.1                                                      13.4         6.63    26.5                                                      15.9         5.57    9.3                                                       17.3         5.12    73.1                                                      17.8         4.97    13.8                                                      21.2         4.19    42.3                                                      21.9         4.06    100.0                                                     26.8         3.32    21.2                                                      28.5         3.13    22.1                                                      28.8         3.10    18.6                                                      32.1         2.79    42.8                                                      34.9         2.59    8.1.                                                      ______________________________________                                    


20. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table N given in claim
 1. 21. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table O given in claim
 1. 22. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table P given in claim
 1. 23. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table Q given in claim
 1. 24. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table R given in claim
 1. 25. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table S given in claim
 1. 26. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table T given in claim
 1. 27. The crystalline molecular sieves of claim 26 wherein the X-ray powder diffraction pattern set forth in Table T contains at least the d-spacings set forth in the following Table TA:

                  TABLE TA                                                         ______________________________________                                         (GeAPSO-43)                                                                                         Relative Intensity                                        2θ     d(Å)                                                                               100 × I/I.sub.o                                     ______________________________________                                         12.4         7.133   100                                                       16.9         5.249   6.2                                                       21.0         4.238   31.8                                                      21.8         4.084   83.5                                                      23.9         3.722   4.6                                                       27.0         3.304   96.5                                                      28.6         3.120   21.0                                                      32.5         2.756   30.1                                                      44.9         2.016   10.2.                                                     ______________________________________                                    


28. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table U given in claim
 1. 29. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V given in claim
 1. 30. The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table W given in claim
 1. 31. Process for preparing crystalline molecular sieves having three-dimensional microporous framework structures of GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂ wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to H and J to W:

                  TABLE A                                                          ______________________________________                                         (GeAPSO-5)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-7.7      12.28-11.48                                                                              m-vs                                                    19.4-19.9    4.58-4.46 w-m                                                     20.85-21.3   4.26-4.17 w-vs                                                    22.1-22.6    4.02-3.93 m-vs                                                    25.6-26.2    3.480-3.402                                                                              vw-m                                                    ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GeAPSO-11)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.8-8.2     11.19-10.85                                                                              m-s                                                      9.0-9.8     9.83-9.03 vw-vs                                                    19.9-20.5   4.46-4.33 m-s                                                      20.8-21.8   4.27-4.08 m-vs                                                     22.0-22.6   4.04-3.93 m-vs                                                     22.6-23.1   3.93-3.85 vw-vs                                                    23.1-23.5   3.85-3.79 w-vs                                                     ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GeAPSO-14)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.6-8.9     10.3-9.93 vs                                                       13.0        6.81      w                                                        21.9-22.2   4.06-4.00 w                                                        25.4        3.51      w                                                        27.5        3.24      w                                                        29.7        3.01      w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GeAPSO-16)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         11.3-11.6   7.83-7.63 w-vs                                                     18.55-18.9  4.78-4.70 vw-m                                                     21.85-22.2  4.07-4.00 m-vs                                                     22.8-23.3   3.900-3.818                                                                              w-m                                                      26.4-27.3   3.370-3.267                                                                              w-m                                                      29.6-29.9   3.018-2.988                                                                              w-m                                                      ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GeAPSO-17)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.70-7.75   11.5-11.4 vs                                                       13.4        6.61      s-vs                                                      15.5-15.55 5.72-5.70 s                                                        19.65-19.7  4.52-4.51 w-s                                                      20.5-20.6   4.33-4.31 vs                                                       31.8-32.0   2.812-2.797                                                                              w-s                                                      ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GeAPSO-18)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                          9.6-9.65   9.21-9.16 vs                                                        15.5-15.55 5.72-5.70 m                                                        16.9-17.1   5.25-5.19 m                                                        20.15-20.25 4.41-4.39 m                                                        20.95-21.05 4.24-4.22 m                                                        31.8-32.5   2.814-2.755                                                                              m                                                        ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GeAPSO-20)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         13.8-14.2   6.42-6.23 m-vs                                                      19.6-20.15 4.53-4.41 m                                                        24.1-24.8   3.695-3.603                                                                              m-vs                                                     27.9-28.6   3.198-3.121                                                                              w                                                         31.3-32.05 2.861-2.791                                                                              w                                                        34.35-35.0  2.610-2.601                                                                              w-m                                                      ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GeAPSO-31)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.4-9.5     10.53-9.31                                                                               w-s                                                      20.2-20.4   4.40-4.35 m                                                        22.0-22.1   4.040-4.022                                                                              m                                                        22.5-22.7   3.952-3.92                                                                               vs                                                       31.6-31.8   2.831-2.814                                                                              w-m                                                      ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         9.25-9.55    9.56-9.26                                                                               w-m                                                      12.5-12.9    7.08-6.86                                                                               vs                                                       16.9-17.3    5.25-5.13                                                                               w-m                                                      20.45-20.9   4.34-4.25                                                                               w-m                                                      23.85-24.25  3.73-3.67                                                                               w-m                                                      26.05-26.35  3.42-3.38                                                                               w-m                                                      27.3-27.6    3.27-3.23                                                                               vs                                                       ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         13.15-13.4   6.73-6.61                                                                               vs                                                       18.05-18.35  4.91-4.83                                                                               m                                                        18.4-18.6    4.82-4.77                                                                               m                                                        26.55-26.7   3.36-3.34                                                                               m                                                        32.0-32.1    2.80-2.79                                                                               m                                                        ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GeAPSO-34)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.3-9.8     9.51-9.03 m-vs                                                     12.6-13.2   7.03-6.71 w-m                                                      15.8-16.3   5.61-5.44 vw-m                                                     20.25-21.2  4.39-4.19 w-vs                                                     24.8-25.4    3.59-3.507                                                                              vw-m                                                     30.0-30.9   2.979-2.894                                                                              vw-m                                                     ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GeAPSO-35)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.6-11.1    8.35-7.97 vw-vs                                                   13.1-13.7    6.76-6.46 vw-vs                                                   17.0-17.6    5.22-5.04 w-s                                                      20.6-21.25  4.31-4.18 vw-m                                                    21.6-22.3    4.11-3.99 m-vs                                                    28.1-28.8    3.175-3.100                                                                              vw-m                                                    ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GeAPSO-36)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.45-8.0    11.14-11.05                                                                              vs                                                       8.1-8.3     10.91-10.65                                                                              w-m                                                      16.3-16.6   5.44-5.34 w-m                                                      18.9-19.4   4.70-4.57 w-m                                                      20.7-21.0   4.29-4.23 w-m                                                      ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GeAPSO-37)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GeAPSO-39)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m                                                       13.1-13.5    6.76-6.56 m                                                       17.8-18.4    4.98-4.82 w-m                                                     20.8-21.3    4.27-4.17 m-vs                                                     22.2-22.85   4.00-3.892                                                                              m-vs                                                     26.4-27.05  3.376-3.296                                                                              w-m                                                     ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GeAPSO-40)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.5-7.7      11.79-11.48                                                                              vw-m                                                    8.0-8.1      11.05-10.94                                                                              s-vs                                                    12.4-12.5    7.14-7.08 w-vs                                                    13.6-13.8    6.51-6.42 m-s                                                     14.0-14.1    6.33-6.28 w-m                                                     27.8-28.0    3.209-3.187                                                                              w-m                                                     ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GeAPSO-41)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.6-13.8    6.51-6.42 w-m                                                     20.5-20.6    4.33-4.31 w-m                                                     21.1-21.3    4.21-4.17 vs                                                      22.1-22.3    4.02-3.99 m-s                                                     22.8-23.0    3.90-3.86 m                                                       23.1-23.4    3.82-3.80 w-m                                                     25.5-25.9    3.493-3.44                                                                               w-m                                                     ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GeAPSO-42)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.15-7.4     12.36-11.95                                                                               m-vs                                                   12.5-12.7    7.08-6.97 m-s                                                     21.75-21.9   4.09-4.06 m-s                                                      24.1-24.25  3.69-3.67 vs                                                      27.25-27.4   3.273-3.255                                                                              s                                                       30.05-30.25  2.974-2.955                                                                              m-s                                                     ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GeAPSO-43)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         12.3-12.95   7.20-6.83 m-vs                                                    16.8-17.45   5.28-5.09 vw-w                                                    21.45-21.85  4.145-4.071                                                                              m-vs                                                    27.0-27.85   3.297-3.232                                                                              w-vs                                                    32.4-33.2    2.763-2.699                                                                              vw-m                                                    ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GeAPSO-44)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m-vs                                                    15.9-16.3    5.57-5.44 vw-m                                                    20.5-21.0    4.33-4.23 m-vs                                                    24.3-25.1    3.66-3.548                                                                               w-m                                                     30.5-31.1    2.931-2.876                                                                              vw-m                                                    ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GeAPSO-46)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-8.1      12.28-10.92                                                                              vs                                                      12.9-13.6    6.86-6.51 vw                                                      21.2-22.2     4.19-4.501                                                                              vw-m                                                     22.5-23.45   3.95-3.793                                                                              vw-m                                                    26.6-27.9    3.351-3.198                                                                              vw-m                                                    ______________________________________                                    

the process comprising providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieves, said reaction mixture composition being expressed in terms of molar oxide ratios as follows: aR:(Ge_(r) Al_(s) P_(t) Si_(u))O₂ :bH₂ Owherein "R" is an organic templating agent; "a" is the amount of "R" and is an effective amount greater than zero to about 6; "b" has a value of from zero to about 500; and "r", "s", "t" and "u" represent the mole fractions, respectively, of germanium, aluminum, phosphorus and silicon in the (Ge_(r) Al_(s) P_(t) Si_(u))O₂ constituent, and each has a value of at least 0.01.
 32. Process according to claim 31 wherein "r", "s", "t" and "u" are within the area defined by points F, G, H, I and J of FIG.
 3. 33. Process according to claim 31 wherein "a" is not greater than about 0.5.
 34. Process according to claim 31 wherein "b" is from about 2 to about
 500. 35. Process according to claim 34 wherein "b" is from about 2 to about
 300. 36. Process according to claim 35 wherein "b" is not greater than about
 20. 37. Process according to claim 36 wherein "b" is not greater than about
 10. 38. Process according to claim 31 wherein the reaction mixture composition contains from about 0.2 to about 0.3 total moles of germanium and silicon per mole of phosphorus.
 39. Process according to claim 31 wherein the reaction mixture composition contains from about 0.75 to about 1.25 moles of aluminum per mole of phosphorus.
 40. Process according to claim 31 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
 41. Process according to claim 31 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxides.
 42. Process according to claim 41 wherein the aluminum alkoxide is aluminum isopropoxide or aluminum tri-sec-butoxide.
 43. Process according to claim 31 wherein the silicon source is silica.
 44. Process according to claim 31 wherein the silica source is a tetraalkyl orthosilicate.
 45. Process according to claim 44 wherein the silica source is tetraethyl orthosilicate.
 46. Process according to claim 31 wherein the source of germanium is selected from the group consisting of oxides, hydroxides, alkoxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates and mixtures thereof.
 47. Process according to claim 46 wherein the source of germanium is germanium tetrachloride or germanium ethoxide.
 48. Process according to claim 31 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
 49. Process according to claim 31 wherein the organic templating agent is an amine.
 50. Process according to claim 31 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diaziabicyclo (2,2,2) octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein x is a value of at least
 2. 51. Molecular sieves prepared by calcining, at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system, the crystalline molecular sieves having three-dimensional microporous framework structures of GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂ wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to H and J to W:

                  TABLE A                                                          ______________________________________                                         (GeAPSO-5)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-7.7      12.28-11.48                                                                              m-vs                                                    19.4-19.9    4.58-4.46 w-m                                                     20.85-21.3   4.26-4.17 w-vs                                                    22.1-22.6    4.02-3.93 m-vs                                                    25.6-26.2    3.480-3.402                                                                              vw-m                                                    ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (GeAPSO-11)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.8-8.2     11.19-10.85                                                                              m-s                                                      9.0-9.8     9.83-9.03 vw-vs                                                    19.9-20.5   4.46-4.33 m-s                                                      20.8-21.8   4.27-4.08 m-vs                                                     22.0-22.6   4.04-3.93 m-vs                                                     22.6-23.1   3.93-3.85 vw-vs                                                    23.1-23.5   3.85-3.79 w-vs                                                     ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (GeAPSO-14)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.6-8.9     10.3-9.93 vs                                                       13.0        6.81      w                                                        21.9-22.2   4.06-4.00 w                                                        25.4        3.51      w                                                        27.5        3.24      w                                                        29.7        3.01      w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (GeAPSO-16)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         11.3-11.6   7.83-7.63 w-vs                                                     18.55-18.9  4.78-4.70 vw-m                                                     21.85-22.2  4.07-4.00 m-vs                                                     22.8-23.3   3.900-3.818                                                                              w-m                                                      26.4-27.3   3.370-3.267                                                                              w-m                                                      29.6-29.9   3.018-2.988                                                                              w-m                                                      ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (GeAPSO-17)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.70-7.75   11.5-11.4 vs                                                       13.4        6.61      s-vs                                                      15.5-15.55 5.72-5.70 s                                                        19.65-19.7  4.52-4.51 w-s                                                      20.5-20.6   4.33-4.31 vs                                                       31.8-32.0   2.812-2.797                                                                              w-s                                                      ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (GeAPSO-18)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                          9.6-9.65   9.21-9.16 vs                                                        15.5-15.55 5.72-5.70 m                                                        16.9-17.1   5.25-5.19 m                                                        20.15-20.25 4.41-4.39 m                                                        20.95-21.05 4.24-4.22 m                                                        31.8-32.5   2.814-2.755                                                                              m                                                        ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (GeAPSO-20)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         13.8-14.2   6.42-6.23 m-vs                                                      19.6-20.15 4.53-4.41 m                                                        24.1-24.8   3.695-3.603                                                                              m-vs                                                     27.9-28.6   3.198-3.121                                                                              w                                                         31.3-32.05 2.861-2.791                                                                              w                                                        34.35-35.0  2.610-2.601                                                                              w-m                                                      ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (GeAPSO-31)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         8.4-9.5     10.53-9.31                                                                               w-s                                                      20.2-20.4   4.40-4.35 m                                                        22.0-22.1   4.040-4.022                                                                              m                                                        22.5-22.7   3.952-3.92                                                                               vs                                                       31.6-31.8   2.831-2.814                                                                              w-m                                                      ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         9.25-9.55    9.56-9.26                                                                               w-m                                                      12.5-12.9    7.08-6.86                                                                               vs                                                       16.9-17.3    5.25-5.13                                                                               w-m                                                      20.45-20.9   4.34-4.25                                                                               w-m                                                      23.85-24.25  3.73-3.67                                                                               w-m                                                      26.05-26.35  3.42-3.38                                                                               w-m                                                      27.3-27.6    3.27-3.23                                                                               vs                                                       ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (GeAPSO-33)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         13.15-13.4   6.73-6.61                                                                               vs                                                       18.05-18.35  4.91-4.83                                                                               m                                                        18.4-18.6    4.82-4.77                                                                               m                                                        26.55-26.7   3.36-3.34                                                                               m                                                        32.0-32.1    2.80-2.79                                                                               m                                                        ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (GeAPSO-34)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.3-9.8     9.51-9.03 m-vs                                                     12.6-13.2   7.03-6.71 w-m                                                      15.8-16.3   5.61-5.44 vw-m                                                     20.25-21.2  4.39-4.19 w-vs                                                     24.8-25.4    3.59-3.507                                                                              vw-m                                                     30.0-30.9   2.979-2.894                                                                              vw-m                                                     ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (GeAPSO-35)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.6-11.1    8.35-7.97 vw-vs                                                   13.1-13.7    6.76-6.46 vw-vs                                                   17.0-17.6    5.22-5.04 w-s                                                      20.6-21.25  4.31-4.18 vw-m                                                    21.6-22.3    4.11-3.99 m-vs                                                    28.1-28.8    3.175-3.100                                                                              vw-m                                                    ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (GeAPSO-36)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.45-8.0    11.14-11.05                                                                              vs                                                       8.1-8.3     10.91-10.65                                                                              w-m                                                      16.3-16.6   5.44-5.34 w-m                                                      18.9-19.4   4.70-4.57 w-m                                                      20.7-21.0   4.29-4.23 w-m                                                      ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (GeAPSO-37)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (GeAPSO-39)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m                                                       13.1-13.5    6.76-6.56 m                                                       17.8-18.4    4.98-4.82 w-m                                                     20.8-21.3    4.27-4.17 m-vs                                                     22.2-22.85   4.00-3.892                                                                              m-vs                                                     26.4-27.05  3.376-3.296                                                                              w-m                                                     ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (GeAPSO-40)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.5-7.7      11.79-11.48                                                                              vw-m                                                    8.0-8.1      11.05-10.94                                                                              s-vs                                                    12.4-12.5    7.14-7.08 w-vs                                                    13.6-13.8    6.51-6.42 m-s                                                     14.0-14.1    6.33-6.28 w-m                                                     27.8-28.0    3.209-3.187                                                                              w-m                                                     ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (GeAPSO-41)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.6-13.8    6.51-6.42 w-m                                                     20.5-20.6    4.33-4.31 w-m                                                     21.1-21.3    4.21-4.17 vs                                                      22.1-22.3    4.02-3.99 m-s                                                     22.8-23.0    3.90-3.86 m                                                       23.1-23.4    3.82-3.80 w-m                                                     25.5-25.9    3.493-3.44                                                                               w-m                                                     ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (GeAPSO-42)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.15-7.4     12.36-11.95                                                                               m-vs                                                   12.5-12.7    7.08-6.97 m-s                                                     21.75-21.9   4.09-4.06 m-s                                                      24.1-24.25  3.69-3.67 vs                                                      27.25-27.4   3.273-3.255                                                                              s                                                       30.05-30.25  2.974-2.955                                                                              m-s                                                     ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (GeAPSO-43)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         12.3-12.95   7.20-6.83 m-vs                                                    16.8-17.45   5.28-5.09 vw-w                                                    21.45-21.85  4.145-4.071                                                                              m-vs                                                    27.0-27.85   3.297-3.232                                                                              w-vs                                                    32.4-33.2    2.763-2.699                                                                              vw-m                                                    ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (GeAPSO-44)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m-vs                                                    15.9-16.3    5.57-5.44 vw-m                                                    20.5-21.0    4.33-4.23 m-vs                                                    24.3-25.1    3.66-3.548                                                                               w-m                                                     30.5-31.1    2.931-2.876                                                                              vw-m                                                    ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (GeAPSO-46)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-8.1      12.28-10.92                                                                              vs                                                      12.9-13.6    6.86-6.51 vw                                                      21.2-22.2     4.19-4.501                                                                              vw-m                                                     22.5-23.45   3.95-3.793                                                                              vw-m                                                    26.6-27.9    3.351-3.198                                                                              vw-m                                                    ______________________________________                                    

                  TABLE W                                                          ______________________________________                                         (GeAPSO-47)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.4-9.6      9.41-9.21 vs                                                      12.8-13.1    6.92-6.76 vw-m                                                    16.0-16.3    5.54-5.44 vw-m                                                    20.5-21.0    4.31-4.23 m-vs                                                    24.6-25.3    3.613-3.526                                                                              vw-m                                                    30.6-31.1    2.921-2.876                                                                              vw-m.                                                   ______________________________________                                    


52. Crystalline molecular sieves comprising three-dimensional microporous framework structures of GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂ wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG.
 1. 53. Molecular sieves according to claim 52 wherein the mole fractions of germanium, aluminum, phosphorus and silicon present as tetrahedral oxides are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG.
 2. 54. Molecular sieves according to claim 53 wherein the mole fractions of germanium, aluminum, phosphorus and silicon present as tetrahedral oxides are within the hexagonal compositional area defined by points g, h, i, j, k and l of FIG.
 2. 55. Molecular sieves according to claim 52 or 53 wherein "m" is not greater than about 0.15.
 56. Process for preparing crystalline molecular sieves having three-dimensional microporous framework structures of GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:mR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂ wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, wherein the process comprises providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieves, said reaction mixture composition being expressed in terms of molar oxide ratios as follows: aR:(Ge_(w) Al_(x) P_(y) Si_(z))O₂ :bH₂ Owherein "R" is an organic templating agent; "a" is the amount of "R" and is an effective amount greater than zero to about 6; "b" has a value of from zero to about 500; and "w", "x", "y" and "z" represent the mole fractions, respectively, of germanium, aluminum, phosphorus and silicon in the (Ge_(w) Al_(x) P_(y) Si_(z))O₂ constituent, and each has a value of at least 0.01.
 57. Process according to claim 56 wherein "r", "s", "t" and "u" are within the area defined by points F, G, H, I and J of FIG.
 3. 58. Process according to claim 56 wherein "a" is not greater than about 0.5.
 59. Process according to claim 56 wherein "b" is from about 2 to about
 500. 60. Process according to claim 59 wherein "b" is from about 2 to about
 300. 61. Process according to claim 60 wherein "b" is not greater than about
 20. 62. Process according to claim 61 wherein "b" is not greater than about
 10. 63. Process according to claim 56 wherein the reaction mixture composition contains from about 0.2 to about 0.3 total moles of germanium and silicon per mole of phosphorus.
 64. Process according to claim 56 wherein the reaction mixture contains from about 0.75 to about 1.25 moles of aluminum per mole of phosphorus.
 65. Process according to claim 56 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
 66. Process according to claim 56 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxides.
 67. Process according to claim 66 wherein the aluminum alkoxide is aluminum isopropoxide or aluminum tri-sec-butoxide.
 68. Process according to claim 56 wherein the silicon source is silica.
 69. Process according to claim 56 wherein the silica source is a tetraalkyl orthosilicate.
 70. Process according to claim 69 wherein the silica source is tetraethyl orthosilicate.
 71. Process according to claim 56 wherein the source of germanium is selected from the group consisting of oxides, hydroxides, alkoxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates and mixtures thereof.
 72. Process according to claim 71 wherein the source of germanium is germanium tetrachloride or germanium ethoxide.
 73. Process according to claim 56 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
 74. Process according to claim 56 wherein the organic templating agent is an amine.
 75. Process according to claim 56 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diaziabicyclo (2,2,2) octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein x has a value of at least
 2. 76. Molecular sieves prepared by calcining, at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system, the crystalline molecular sieves having three-dimensional microporous framework structures of GeO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:mR:(Ge_(r) Al_(s) P_(t) Si_(u))O₂ wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Ge_(r) Al_(s) P_(t) Si_(u))O₂ and has a value of zero to about 0.3; and "r", "s", "t" and "u" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG.
 1. 